Herbicidal mixtures containing picolinafen

ABSTRACT

A herbicidal mixture, comprising
     A) picolinafen (I)   

     
       
         
         
             
             
         
       
         
         
           
             or an agriculturally useful salt thereof,
 
and
 
           
         
         B) at least one further herbicide selected from the group of the phthalamates (B1), semicarbazones (B2), chloracetanilides (B3), carbamates (B4), pyridazines (B5), dinitrophenols (B6), dipyridylenes (B7), benzothiadiazoles (B8), uracils (B9), pyridazinones (B10), phenylcarbamates (B11), benzoic acids (B12), quinolinecarboxylic acids (B13), nitriles (B14), benzamides (B15) and amides (B16).

CROSS REFERENCE TO RELATED APPLICATION

This application is a 35 USC §371 National Phase Entry Application fromPCT/EP2004/002633, filed Mar. 12, 2004, and designating the UnitedStates, which claims the benefit of U.S. Provisional 60/453,975, filedMar. 13, 2003.

The present invention relates to a herbicidal mixture comprising

-   A) picolinafen (I)

-   -   or the agriculturally useful salts thereof;        and

-   B) at least one further herbicide selected from the group of the    phthalamates (B1), semicarbazones (B2), chloroacetanilides (B3),    carbamates (B4), pyridazines (B5), dinitrophenols (B6),    dipyridylenes (B7), benzothiadiazoles (B8), uracils (B9),    pyridazinones (B10), phenylcarbamates (B11), benzoic acids (B12),    quinolinecarboxylic acids (B13), nitriles (B14), benzamides (B15)    and amides (B16);    and if desired

-   C) a safener selected from the group consisting of isoxadifen,    mefenpyr and cloquintocet.

Moreover, the invention relates to herbicidal compositions comprising amixture of components A and B and, if desired, component C and at leastone liquid and/or solid carrier and, if desired, at least onesurfactant.

Moreover, the invention relates to processes for preparing thesemixtures or compositions and to methods for controlling unwantedvegetation.

Mixtures of picolinamides with other specific herbicides are known fromWO 94/07368 and WO 01/26466. For crop protection compositions, it isdesirable in principle to increase the specific activity of an activecompound and to enhance the safety of action. It was an object of thepresent invention to increase the activity of picolinafen.

We have found that this object is achieved by the mixtures defined atthe outset. Moreover, we have found herbicidal compositions comprisingthese mixtures and processes for their preparation and methods forcontrolling unwanted vegetation. In the last-mentioned methods it isimmaterial whether components A, B and, if desired, C are formulated andapplied jointly or separately, and, in the case of separate application,in which order the application is carried out.

The mixtures according to the invention show a synergistic effect; thecompatibility of the herbicidally active components A) and B) withcertain crop plants is generally maintained. However, it may bedesirable to employ a component C) in an amount where a safening effectis observed.

Examples of herbicides which can be used in combination with picolinafen(A) and, if desired, component C) in accordance with the presentinvention are, inter alia:

-   B1: phthalamates, for example:    -   naptalam;-   B2: semicarbazones, for example:    -   diflufenzopyr;-   B3: chloroacetanilides, for example:    -   dimethenamid, S-dimethenamid, acetochlor, alachlor, butachlor,        butenachlor,    -   diethatyl-ethyl, dimethachlor, metazachlor, metolachlor,        S-metolachlor,    -   pretilachlor, propachlor, prynachlor, terbuchlor, thenylchlor or        xylachlor;-   B4: carbamates, for example:    -   asulam, carbetamid, chlorpropham, orbencarb, pronamid, propham        or tiocarbazil;-   B5: pyridazines, for example:    -   dithiopyr or thiazopyr;-   B6: dinitrophenols, for example:    -   bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, or DNOC;-   B7: dipyridylenes, for example:    -   cyperquat, difenzoquat, diquat or paraquat;-   B8: benzothiadiazoles, for example:    -   bentazone;-   B9: uracils, for example:    -   bromacil, isocil, lenacil or terbacil;-   B10: pyridazinones, for example:    -   chloridazon;-   B11: phenylcarbamates, for example:    -   desmedipham or phenmedipham;-   B12: benzoic acids, for example:    -   chloramben or dicamba;-   B13: quinolinecarboxylic acids, for example:    -   quinchlorac or quinmerac;-   B14: nitriles, for example:    -   dichlorbenil or chlorthiamid;-   B15: benzamides, for example:    -   isoxaben;-   B16: amides, for example:    -   allidochlor, benzoyl-ethyl, bromobutide, diphenamid, etobenzanid        (benzochlomet), fosamine or monalide;        and the agriculturally useful salts thereof, or, if the compound        is a carboxylic acid, the agriculturally useful esters,        thioesters or amides thereof.

Picolinafen is known from EP 447 004.

The herbicides of component B) are known from

-   -   “Herbizide” [Herbicides], B. Hock, C. Fedtke, R. R. Schmidt,        1^(st) edition, Thieme 1995 (quinchlorac (p. 238), butachlor (p.        32), pretilachlor (p. 32), di-thiopyr (p. 32), bromobutide (p.        243), bentazone (p. 30), chlorpropham (p. 205);    -   “Agricultural Chemicals”, Book II Herbicides, 1993 (etobenzamid        (HW-52)(p. 54), dimethenamid (p. 48), quinmerac (p. 233),        metazachlor (p. 64), bromofenoxim (p. 228), thiazopyr (p. 226));    -   “Agricultural Chemicals”, Book II Herbicides, 13^(th) Edition        (diflufenzopyr (p. 90), butenachlor (p. 54) tiocarbazil (p.        84));    -   Farm Chemicals Handbook 1994, Meister Publishing Company 1994        (isocil (p. C.200));    -   “Short Review of Herbicides & PGRs” 1991, Hodogaya Chemicals        (thenylchlor (NSK-850) (p. 52), allidochlor (p. 48),        benzoylprop-ethyl (p. 38), chlorthiamid (p. 150), diphenamid (p.        34), fosamine (p. 232), isoxaben (p. 42), monalide (p. 32),        napthalam (p. 36), pronamid (p. 34), chloramben (p. 28), dicamba        (p. 26), asulam (p. 112), carbetamid (p. 36), desmedipham (p.        104), orbencarb (p. 112), phenmedipham (p. 104), propham (p.        100), acetochlor (p. 48), alachlor (p. 46), diethathyl-ethyl (p.        48), demethachlor (p. 50), metolachlor (p. 46), propachlor (p.        44), prynachlor (p. 44), terbuchlor (p. 48), xylachlor (p. 52),        dinoseb (p. 128), dinoseb-acetate (p. 128), dinoterb (p. 128),        DNbC (p. 126), cyperquat-chloride (p. 158), difenzoquat (p.        160), diquat (p. 158), paraquat (p. 158), chloridazon (p. 174),        bromacil (p. 180), lenacil (p. 180), terbacil (p. 180),        dichlorbenil (p. 148), terbuchlor (p. 48)).

The safeners of component C) are known from

-   -   B. Hock, C. Fedtke, R. R. Schmidt, 1^(st) edition, Thieme 1995        (cloquinocet (p. 266));    -   Agrow 293 (11.28.97) (mefenpyr);    -   Agrow 324 (03.12.99) (isoxadifen).

The active compounds of the present invention can be present and usedboth in the form of the pure enantiomers and as racemates ordiastereomer mixtures.

Furthermore, the active compounds can be used in the form of theiragriculturally useful salts and, if the compounds are carboxylic acids,also in the form of their agriculturally useful esters, thioesters andamides.

Suitable salts are, in general, the salts of those cations, the acidaddition salts of those acids or the esters, thioesters and amides whosecations or anions or esters, thioesters and amides have no adverseeffect on the herbicidal action or the safening action.

Suitable cations are in particular alkali metal cations, such aslithium, sodium or potassium, or alkaline earth metal cations, such asmagnesium or calcium. Also suitable are organic cations, such asphosphonium ions, sulfonium ions, preferably tri-(C₁-C₄-alkyl)sulfonium,such as trimethylsulfonium, sulfoxonium ions, preferablytri-(C₁-C₄-alkyl)sulfoxonium. Likewise suitable is ammonium, where, ifdesired, one to four hydrogen atoms can be replaced by C₁-C₄-alkyl,hydroxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl or benzyl, preferably ammonium,methylammonium, dimethylammonium, trimethylammonium,tetramethylammonium, tetraethylammonium, isopropylammonium,diisopropylammonium, tetrabutyl-ammonium, ethanolammonium,diethanolammonium, 2-(2-hydroxyethoxy)ethyl-ammonium,benzyltrimethylammonium or benzyltriethylammonium.

Anions of useful acid addition salts are primarily halides, such asfluorides, chlorides, bromides or iodides, nitrates, hydrogensulfates,sulfates, dihydrogenphosphates, hydrogenphosphates, phosphates,methylsulfates, bicarbonates and carbonates.

Suitable esters are, for example, straight-chain or branchedC₁-C₁₀-alkyl esters, in particular methyl, ethyl, propyl, isopropyl,butyl, isobutyl or isooctyl esters, or straight-chain or branchedC₁-C₄-alkoxy-C₁-C₄-alkyl esters, in particular methoxyethyl, ethoxyethylor butoxyethyl esters. Examples of thioesters are straight-chain orbranched C₁-C₁₀-alkylthio esters, in particular ethylthio esters.Suitable for use as amides are, inter alia, methyl- or dimethylamides,and also anilides, such as anilide itself or 2-chloroanilide.

In a preferred embodiment, the herbicidal mixture according to theinvention comprises

-   A) picolinafen or an agriculturally useful salt thereof;    and-   B) at least one further herbicide selected from the group of    -   B1: phthalamates, for example:        -   naptalam;    -   B2: semicarbazones, for example:        -   diflufenzopyr;    -   B3: chloroacetanilides, for example:        -   dimethenamid, S-dimethenamid, acetochlor, alachlor,            butachlor,        -   butenachlor, diethatyl-ethyl, dimethachlor, metazachlor,            metolachlor,        -   S-metolachlor, pretilachlor, propachlor, prynachlor,            terbuchlor, thenylchlor or xylachlor;    -   B4: carbamates, for example:        -   asulam, carbetamid, chlorpropham, orbencarb, pronamid,            propham or tiocarbazil;    -   B5: pyridazines, for example:        -   dithiopyr or thiazopyr;    -   B6: dinitrophenols, for example:        -   bromofenoxim, dinoseb, dinoseb-acetate, dinoterb or DNOC;    -   B7: dipyridylenes, for example:        -   cyperquat, difenzoquat, diquat or paraquat;    -   B8: benzothiadiazoles, for example:        -   bentazone;    -   B9: uracils, for example:        -   bromacil, isocil, lenacil or terbacil;    -   B10: pyridazinones, for example:        -   chloridazon;    -   B11: phenylcarbamates, for example:        -   desmedipham or phenmedipham;    -   B12: benzoic acids, for example:        -   chloramben or dicamba;    -   B13: quinolinecarboxylic acids, for example:        -   quinchlorac or quinmerac;    -   B14: nitriles, for example:        -   dichlorbenil or chlorthiamid;    -   B15: benzamides, for example:        -   isoxaben;    -   B16: amides, for example:        -   allidochlor, benzoyl-ethyl, bromobutide, diphenamid,            etobenzanid (benzochlomet), fosamine or monalide;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof.

In a particularly preferred embodiment, the herbicidal mixture accordingto the invention comprises

-   A) picolinafen or an agriculturally useful salt thereof    and-   B) at least one further herbicide selected from the group consisting    of    -   B7: dipyridylenes, for example        -   cyperquat, difenzoquat, diquat or paraquat;    -   B8: benzothiadiazoles, for example        -   bentazone;    -   B9: uracils, for example        -   bromacil, isocil, lenacil or terbacil;    -   B12: benzoic acids, for example        -   chloramben or dicamba;    -   B13: quinolinecarboxylic acids, for example        -   quinchlorac or quinmerac, in particular quinchlorac;    -   B15: benzamides, for example        -   isoxaben;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof.

In an especially preferred embodiment, the herbicidal mixture accordingto the invention comprises

-   A) picolinafen or an agriculturally useful salt thereof    and-   B) at least one further herbicide selected from the group consisting    of    -   B7: dipyridylenes, for example        -   cyperquat, difenzoquat, diquat or paraquat;    -   B8: benzothiadiazoles, for example        -   bentazone;    -   B12: benzoic acids, for example        -   chloramben or dicamba;    -   B15: benzamides, for example        -   isoxaben;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof.

Extraordinary preference is given to herbicidal mixtures comprisingpicolinafen+difenzoquat, picolinafen+paraquat, picolinafen+bentazone,picolinafen+isocil, picolinafen+dicamba, picolinafen+quinchlorac,picolinafen+quinmerac or picolinafen+isoxaben.

In a most extraordinary embodiment, the herbicidal mixture comprisespicolinafen+difenzoquat, picolinafen+bentazone, picolinafen+dicamba orpicolinafen+isoxaben.

If the mixture comprises the active compounds paraquat or difenzoquat,preference is also given to those mixtures in which the active compoundsmentioned above are present as chloride, bromide or methylsulfate salts.

If the mixture comprises the active compounds bentazone, dicamba orquinchlorac, preference is also given to those mixtures in which theactive compounds mentioned above are present as trimethylsulfonium,ammonium, sodium, potassium, magnesium or calcium salts.

If the mixture comprises the active compounds dicamba or quinchlorac,preference is also given to those mixtures in which the active compoundsmentioned above are replaced by their ethanolammonium,diethanolammonium, methylammonium, dimethylammonium, trimethylammonium,isopropylammonium or 2-(2-hydroxyethoxy)-ethylammonium salts, theirmethyl- or dimethylamides, their anilides or 2-chloro-anilides, theirmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, isooctyl,methoxyethyl, ethoxyethyl, butoxyethyl esters or their ethyl thioesters.

In a further preferred embodiment, the herbicidal mixture according tothe invention comprises

-   A) picolinafen or an agriculaturally useful salt thereof;    and-   B) at least one further herbicide selected from the group consisting    of    -   B8: benzothiadiazoles, for example        -   bentazone;    -   B12: benzoic acids, for example        -   chloramben or dicamba;    -   B13: quinolinecarboxylic acids, for example        -   quinchlorac or quinmerac;    -   B15: benzamides, for example        -   isoxaben;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof.

Extraordinary preference is given to herbicidal mixtures comprisingpicolinafen+quinchlorac, picolinafen+quinmerac or pincolinofen+isoxaben.

If the mixture comprises the active compounds bentazone, dicamba,quinchlorac or quinmerac, preference is also given to those mixtures inwhich the active compounds above are present as trimethylsulfonium,ammonium, sodium, potassium, magnesium or calcium salts.

If the mixture comprises the active compounds dicamba, quinchlorac orquinmerac, preference is also given to those mixtures in which theactive compounds mentioned are replaced by their ethanolammonium,dimethanolammonium, methylammonium, dimethylammonium, trimethylammonium,isopropylammonium or 2-(2-hydroxyethoxy)-ethylammonium salts, withoutmethyl- or dimethylamides, their anilides or 2-chloro-anilides, and alsomethyl, ethyl, propyl, isopropyl, butyl, isobutyl, isooctyl,methoxy-ethyl, ethoxyethyl, butoxyethyl esters or their ethylthioesters.

In a further particularly preferred embodiment, the herbicidal mixtureaccording to the invention comprises

-   A) picolinafen or an agriculturally useful salt thereof    and-   B) at least one further herbicide, selected from the group    consisting of    -   B2: semicarbazones, for example:        -   diflufenzopyr;    -   B3: chloroacetanilides, for example:        -   acetochlor, diethatyl-ethyl, dimethachlor, prynachlor,            terbuchlor, thenylchlor or xylachlor;    -   B4: carbamates, for example:        -   carbetamid, chlorpropham, pronamid or propham;    -   B6: dinitrophenols, for example:        -   bromofenoxim, dinoseb, dinoseb-acetate or DNOC;    -   B7: dipyridylenes, for example:        -   cyperquat, difenzoquat, diquat or paraquat;    -   B9: uracils, for example:        -   isocil or lenacil;    -   B10: pyridazinones, for example:        -   chloridazon;    -   B11: phenylcarbamates, for example:        -   desmedipham or phenmedipham;    -   B13: quinolinecarboxylic acids, for example:        -   quinchlorac or quinmerac;    -   B15: benzamides, for example:        -   isoxaben;    -   B16: amides, for example:        -   allidochlor, benzoyl-ethyl, diphenamid, etobenzanid            (benzochlomet), fosamine or monalide;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof.

In a particularly extraordinary embodiment, the herbicidal mixtureaccording to the invention comprises picolinafen+difenzoquat orpicolinafen+isoxaben.

In a further particularly preferred embodiment, the herbicidal mixtureaccording to the invention comprises

-   A) picolinafen or an agriculturally useful salt thereof    and-   B) at least one further herbicide, selected from the group    consisting of    -   B1: phthalamates, for example:        -   naptalam;    -   B2: semicarbazones, for example:        -   diflufenzopyr;    -   B3: chloroacetanilides, for example:        -   dimethenamid, S-dimethenamid, acetochlor, alachlor,            butachlor, butenachlor, diethatyl-ethyl, dimethachlor,            metazachlor, metolachlor, S-metolachlor, pretilachlor,            propachlor, prynachlor, terbuchlor, thenylchlor or            xylachlor;    -   B4: carbamates, for example:        -   asulam, carbetamid, chlorpropham, orbencarb, pronamid,            propham or tiocarbazil;    -   B5: pyridazines, for example:        -   dithiopyr or thiazopyr;    -   B6: dinitrophenols, for example:        -   bromofenoxim, dinoseb, dinoseb-acetate, dinoterb or DNOC;    -   B7: dipyridylenes, for example:        -   cyperquat, difenzoquat, diquat or paraquat;    -   B8: benzothiadiazoles, for example:        -   bentazone;    -   B9: uracils, for example:        -   bromacil, isocil, lenacil or terbacil;    -   B10: pyridazinones, for example:        -   chloridazon;    -   B11: phenylcarbamates, for example:        -   desmedipham or phenmedipham;    -   B12: benzoic acids, for example:        -   chloramben or dicamba;    -   B13: quinolinecarboxylic acids, for example:        -   quinchlorac or quinmerac;    -   B14: nitriles, for example:        -   dichlorbenil or chlorthiamid;    -   B15: benzamides, for example:        -   isoxaben;    -   B16: amides, for example:        -   allidochlor, benzoyl-ethyl, bromobutide, diphenamid,            etobenzanid (benzochlomet), fosamine or monalide;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof;        and-   C) a safener selected from the group consisting of isoxadifen,    preferably isoxadifen “acid” or isoxadifen-ethyl, in particular    isoxadifen-ethyl; mefenpyr, preferably mefenpyr “acid” or    mefenpyr-diethyl, in particular mefenpyr-diethyl; and cloquintocet,    preferably doquintocet “acid”, cloquintocet-mexyl or    cloquintocet-mexyl×n hydrate (n=2 to 6), in particular    cloquintocet-mexyl.

In a further particularly preferred embodiment, the herbicidal mixtureaccording to the invention comprises

-   A) picolinafen or an agriculturally useful salt thereof,    and-   B) at least one further herbicide, selected from the group    consisting of    -   B1: phthalamates, for example        -   naptalam;    -   B2: semicarbazones, for example        -   diflufenzopyr;    -   B3: chloroacetanilides, for example        -   dimethenamid, S-dimethenamid, acetochlor, alachlor,            butachlor, butenachlor, diethatyl-ethyl, dimethachlor,            metazachlor, metolachlor, S-metolachlor, pretilachlor,            propachlor, prynachlor, terbuchlor, thenylchlor or            xylachlor;    -   B4: carbamates, for example        -   asulam, carbetamid, chlorpropham, orbencarb, pronamid,            propham or tiocarbazil;    -   B5: pyridazines, for example    -   dithiopyr or thiazopyr;    -   B6: dinitrophenols, for example        -   bromofenoxim, dinoseb, dinoseb-acetate, dinoterb, or DNOC;    -   B10: pyridazinones, for example        -   chloridazon;    -   B11: phenylcarbamates, for example    -   desmedipham or phenmedipham;    -   B14: nitriles, for example        -   dichlorbenil or chlorthiamid;    -   B15: benzamides, for example        -   isoxaben;    -   B16: amides, for example        -   allidochlor, benzoyl-ethyl, bromobutide, diphenamid,            etobenzanid (benzochlomet), fosamine or monalide;    -   and an agriculturally useful salt thereof;        and-   C) a safener selected from the group consisting of isoxadifen,    preferably isoxadifen “acid” or isoxadifen-ethyl, in particular    isoxadifen-ethyl, mefenpyr, preferably mefenpyr “acid” or    mefenpyr-diethyl, in particular mefenpyr-diethyl, and cloquintocet,    preferably cloquintocet “acid”, cloquintocet-mexyl or    cloquintocet-mexyl×n hydrate (n=2 to 6), in particular    cloquintocet-mexyl.

In a further preferred embodiment, the herbicidal mixture comprises

-   A) picolinafen or an agriculturally useful salt thereof;    and-   B) at least one further herbicide selected from the group consisting    of    -   B7: dipyridylenes, for example        -   cyperquat, difenzoquat, diquat or paraquat;    -   B8: benzothiadiazoles, for example    -   bentazone;    -   B9: uraciles, for example        -   bromacil, lenacil, terbacil or isocil;    -   B12: benzoic acids, for example        -   chloramben or dicamba;    -   B13: quinolinecarboxylic acids, for example        -   quinchlorac or quinmerac;    -   and an agriculturally useful salt thereof, or, if the compound        is a carboxylic acid, an agriculturally useful ester, thioester        or amide thereof;        and-   C) a safener selected from the group consisting of isoxadifen,    preferably isoxadifen “acid” or isoxadifen-ethyl, in particular    isoxadifen-ethyl, mefenpyr, preferably mefenpyr “acid” or    mefenpyr-diethyl, in particular mefenpyr-diethyl, and cloquintocet,    preferably cloquintocet “acid”, cloquintocet-mexyl or    cloquintocet-mexyl×n hydrate (n=2 to 6), in particular    cloquintocet-mexyl.

In a particularly preferred embodiment, the herbicidal mixture comprises

-   A) picolinafen or an agriculturally useful salt thereof;    and-   B) at least one further herbicide selected from the group consisting    of difenzoquat, paraquat, bentazone, isocil, dicamba and    quinchlorac; or an agricultural salt thereof, or, if the herbicide    is a carboxylic acid, an agriculturally useful ester, thioester or    amide thereof;    and-   C) isoxadifen-ethyl.

In a further particularly preferred embodiment, the herbicidal mixturecomprises

-   A) picolinafen or an agriculturally useful salt thereof,    and-   B) at least one further herbicide selected from the group consisting    of difenzoquat, paraquat, bentazone, isocil, dicamba and    quinchlorac; or an agricultural salt thereof, or, if the herbicide    is a carboxylic acid, an agriculturally useful ester, thioester or    amide thereof;    and-   C) mefenpyr-diethyl.

In a further particularly preferred embodiment, the herbicidal mixturecomprises

-   A) picolinafen or an agriculturally useful salt thereof;    and-   B) at least one further herbicide selected from the group consisting    of difenzoquat, paraquat, bentazone, isocil, dicamba and    quinchlorac; or an agricultural salt thereof, or, if the herbicide    is a carboxylic acid, an agriculturally useful ester, thioester or    amide thereof;    and-   C) cloquintocet, preferably cloquintocet “acid”, cloquintocet-mexyl    or cloquintocet-mexyl×n hydrate (n=2 to 6), in particular    cloquintocet-mexyl.

In a further preferred embodiment, the herbicidal mixture comprises, inaddition to picolinafen, only one further herbicide selected from thegroup B).

The corresponding preferences apply analogously to what was said above.

In a further preferred embodiment, the herbicidal mixture comprises, inaddition to picolinafen, only one further herbicide selected from groupB) and only one safener selected form group C).

The corresponding preferences apply analogously to what was said above.

Components A and B are applied in a synergistically effective amount;the mixing ratios of components A) to B) are usually within a weightratio of from 1:0.1 to 1:50, preferably from 1:0.2 to 1:20.

If a safener C) is used, too, the mixing ratios of components A) to B)to C) are within a weight ratio of from 1:0.1:0.1 to 1:50:10, preferablyfrom 1:0.2:0.2 to 1:20:4.

The present invention is also directed to herbicidal compositionscomprising a herbicidally effective amount of a herbicidal mixture(comprising components A) and B) and, if desired, C), as describedabove), at least one liquid and/or solid carrier and, if desired, atleast one surfactant.

The herbicidal mixtures and herbicidal compositions according to theinvention allow very good control of broad-leaf weeds and weed grassesin crops such as corn, cereals, rice and soybeans, in particular incereals, without damaging the crop plant; an effect which occurs inparticular also at low application rates.

Taking into account the universality of the application methods, thesynergistic herbicidal mixtures and herbicidal compositions according tothe invention can additionally be employed in a further number of cropplants for eliminating undesirable plants. Examples of suitable cropsare the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napusvar. napus, Brassica napus var. napo-brassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, lpomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta,Medicago sativa, Musa spp., Nicotiana tabacum (N. rustica), Oleaeuropaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Piceaabies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyruscommunis, Ribes sylvestre, Ricinus communis, Saccharum officinarum,Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare),Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum,Vicia faba, Vitis vinifera and Zea mays.

In addition, the herbicidal mixtures and herbicidal compositionsaccording to the invention can also be used in crops which tolerate theaction of herbicides owing to breeding, including genetic engineeringmethods. Suitable are preferably genetically engineered cereals whichare resistant against glyphosate or against herbicidal ALS inhibitors,such as, for example, sulfonylureas or imidazolinones.

The mixtures according to the invention or the herbicidal compositionscomprising them can be used, for example, in the form of directlysprayable aqueous solutions, powders, suspensions, alsohighly-concentrated aqueous, oily or other suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, spreading orwatering.

The use forms depend on the intended purposes; in each case, they shouldensure the finest possible distribution of the active compoundsaccording to the invention.

The herbicidal compositions comprise components A) and B) and, ifdesired, C) and auxiliaries customary for formulating crop protectionagents.

Suitable inert additives are mineral oil fractions of medium to highboiling point, such as kerosene and diesel oil, furthermore coal taroils and oils of vegetable or animal origin, aliphatic, cyclic andaromatic hydrocarbons, for example paraffin, tetrahydro-naphthalene,alkylated naphthalenes or derivatives thereof, alkylated benzenes orderivatives thereof, alcohols, such as methanol, ethanol, propanol,butanol, cyclo-hexanol, ketones, such as cyclohexanone, strongly polarsolvents, such as N-methyl-pyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byadding water. To prepare emulsions, pastes or oil dispersions,components A), B) and, if desired, C), as such or dissolved in an oil orsolvent, can be homogenized in water using a wetting agent, tackifier,dispersant or emulsifier. Alternatively, it is possible to prepareconcentrates comprising active compound, wetting agent, tackifier,dispersant or emulsifier and, if appropriate, solvent or oil, which aresuitable for dilution with water.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, for example ligno-,phenol-, naphthalene- and dibutyinaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ethersulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta-and octadecanols, and also of fatty alcohol glycol ethers, condensatesof sulfonated naphthalene and its derivatives with formaldehyde,condensates of naphthalene or of the naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylatedisooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenylpolyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, laurylalcohol polyglycol ether acetate, sorbitol esters, lignosulfite wasteliquors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing orgrinding the synergistic herbicidal mixture or the individual activecompounds with a solid carrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules can be prepared by binding the active compounds tosolid carriers. Solid carriers are mineral earths, such as silicicacids, silica gels, silicates, talc, kaolin, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas and products of vegetable origin, such as cereal meal,treebark meal, wood meal and nutshell meal, cellulose powders, or othersolid carriers.

The concentrations of the mixtures according to the invention in theready-to-use preparations can be varied within wide ranges. In general,the formulations comprise from about 0.001 to 98% by weight, preferablyfrom 0.01 to 95% by weight, in particular from 0.5 to 90% by weight, ofactive compounds.

The active compounds of components A) and B) and, if desired, C) can beformulated jointly, but also separately, and/or applied jointly orseparately to the plants, their habitat and/or seeds. The activecompounds are preferably applied simultaneously. However, it is alsopossible to apply them separately.

Moreover, it may be useful to apply the herbicidal mixtures orherbicidal compositions according to the invention jointly or separatelywith further crop protection agents, for example with agents forcontrolling pests or phytopathogenic fungi or bacteria. Of interest isfurthermore the miscibility with mineral salt solutions employed fortreating nutritional and trace element deficiencies. Non-phytotoxic oilsand oil concentrates may also be added.

The mixtures and herbicidal compositions according to the invention canbe applied by the pre-emergence or by the post-emergence method. If theactive compounds are less well tolerated by certain crop plants,application techniques may be used in which the herbicidal compositionsare sprayed, with the aid of the spraying equipment, in such a way thatthey come into as little contact as possible, if any, with the leaves ofthe sensitive crop plants, while the active compounds reach the leavesof the undesirable plants growing underneath, or the bare soil surface(post-directed, lay-by).

In the case of post-emergence treatment, the herbicidal compositionsaccording to the invention are applied to the plants mainly by sprayingthe leaves. Here, the application can be carried out by customaryspraying techniques using, for example, water as carrier and amounts ofspray liquor of from about 100 to 1000 I/ha. Application of thecompositions by the low-volume and ultra-low-volume method and theirapplication in the form of granules is also possible.

The required application rate of pure active compound mixture, i.e. A)and B) and, if desired, C), without formulation auxiliary, is, dependingon the composition of the plant stand, and depending on thedevelopmental stages of the plants, the climatic conditions and theapplication technique, in general from 0.001 to 3.0 kg/ha, preferablyfrom 0.01 to 2.5 kg/ha, in particular from 0.01 to 1.0 kg/ha, of activesubstance (a.s.)

The application rate of picolinafen is generally from 0.01 to 0.5 kg/haof active substance (a.s.).

The application rate of component B) is generally from 0.01 to 2.0 kg/haof active substance (a.s.).

The application rate of component C) is generally from 0.01 to 0.5 kg/haof active substance (a.s.).

USE EXAMPLES

The mixtures according to the invention were applied by thepre-emergence method or by the post-emergence method (foliar treatment).

Some of the experiments were greenhouse experiments, while others werecarried out in the open in small plots (on a site with sandy loam soil(pH 6.2 to 7.0) or sandy clay soil (pH 5.0 to 6.7)).

The harmful plants came in different sizes and developmental stages,averaging 5 to 20 cm, depending on their habit.

The herbicidally active compounds of components A) and B) and, ifdesired, the safeners C) were applied in succession or jointly, in thelatter case as a tank mix in some cases and as a readymix in othercases, in the form of emulsions, aqueous solutions or suspensions, thevehicle used being water (300-400 I/ha). In the experiments in the open,application was effected with the aid of a mobile plot sprayer.

The experimental period extended over 3 to 8 weeks; observations on thestand were also made at later points in time.

The damage caused by the herbicidal compositions was assessed using ascale from 0% to 100% in comparison with untreated control plots. 0means no damage and 100 means complete destruction of the plants.

The examples below demonstrate the effect of the herbicidal compositionswhich can be used in accordance with the invention, without excludingthe possibility of other applications.

In these examples, the method of S. R. Colby (Calculating synergisticand antagonistic responses of herbicide combinations, Weeds 15, 20 ff(1967)) was used to calculate the value E which can be expected if theaction of the individual active compounds is merely additive.

The calculation was based on the formula

$E = {X + Y - \frac{XY}{100}}$where

-   X=percentage of the herbicidal action of component A) at an    application rate of a;-   Y=percentage of the herbicidal action of component B) at an    application rate of b;-   E=herbicidal action of components A)+B) to be expected at    application rates a+b (in %).

If the observed value exceeds the value E calculated using Colby'sformula, synergism is present.

The herbicidal mixtures according to the invention, such as, forexample, picolinafen+difenzoquat, picolinafen+bentazone,picolinafen+dicamba or picolinafen+isoxaben, applied at appropriateapplication rates by the post-emergence method, have a more potentherbicidal action than would be expected in accordance with Colby basedon the observed effects of the individual components when used alone.

1. A herbicide, consisting essentially of a synergistic mixture of: A)picolinafen (I)

or an agriculturally useful salt thereof, and B) at least one furtherherbicide selected from the group consisting of dicamba and quinmerac,the agriculturally useful salts thereof and the agriculturally usefulesters, thioesters and amides thereof, and wherein component A) andcomponent B) are present in a weight ratio of from 1:8 to 2:1 forpicolinafen:dicamba or from 1:5 to 1:1.25 for picolinafen:quinmerac. 2.A herbicide as claimed in claim 1, wherein component B) is dicamba orquinmerac.
 3. A herbicidal composition consisting essentially of aherbicidally effective amount of a mixture as claimed in claim 1, atleast one inert liquid and/or solid carrier and, if desired, at leastone surfactant to prepare said composition.
 4. A process for preparingherbicidal compositions as claimed in claim 3, which comprises mixingcomponent A), component B), at least one inert liquid and/or solidcarrier and, if desired, a surfactant.
 5. A method for controllingunwanted vegetation, which comprises simultaneously or successivelyapplying to unwanted plants, their habitat and or seeds a herbicide asclaimed in claim 1 before, during and/or after emergence of the unwantedplants, where components A), B) and, if desired, C), a safener selectedfrom the group consisting of isoxadifen, mefenpyr and cloquintocet, canbe applied jointly or separately.
 6. A method for controlling unwantedvegetation as claimed in claim 5, wherein the herbicide is applied toleaves of crop plants and of the unwanted plants.
 7. A method forcontrolling undesired vegetation comprising simultaneously orsuccessively applying to undesired plants, their habitat or their seedsa synergistic mixture consisting essentially of: A) picolinafen (I)

or an agriculturally useful salt thereof, and B) at least one furtherherbicide selected from the group consisting of dicamba and quinmerac,the agriculturally useful salts thereof and the agriculturally usefulesters, thioesters and amides thereof, and wherein component A) andcomponent B) are present in a weight ratio of from 1:8 to 2:1 forpicolinafen:dicamba or from 1:5 to 1:1.25 for picolinafen:quinmerac. 8.The herbicide of claim 1, further consisting of component C), a safenerselected from the group consisting of isoxadifen, mefenpyr andcloquintocet.
 9. The process as claimed in claim 4, wherein the processfurther includes mixing a safener selected from the group consisting ofisoxadifen, mefenpyr, and cloquintocet with the other components.